Method of preparing starch ether derivatives and new starch ether derivatives produced thereby



United States Patent METHOD OF PREPARING STARCH ETHER DERIV- ATIVES AND NEW STARCH ETHER DERIVA- TIVES PRODUCED THEREBY Erling T. Hjermstad and Carl C. Kesler, Cedar Rapids, Iowa, assignors to' Penick & Ford, Ltd., Incorporated, Cedar Rapids, Iowa, a corporation of Delaware No Drawing. ApplicationFebruary 20, 1952 Serial No. 272,712

Claims. (Cl. 260233.3)

This invention relates to a method of preparing starch ether derivatives and to new starch ether derivatives produced thereby. The new starch ether derivatives produced by the method of this invention are characterized by having the starch in its original, unswollen, granule form, while at the same time being more susceptible to swelling in the presence of water and tending to gelatinize at considerably lower temperatures than unmodified starch of the same type.

Starch occurs in nature in the form of characteristically shaped particles called granules. insoluble in cold water and do not become appreciably hydrated or swollen until the temperature of the water is raised to above 65 C. The insolubility of starch granules in water at lower temperatures is of considerable economic importance because starch occurs in nature in intimate association with other materials such as protein, fiber, mineral salts, oils, and other carbohydrates. Due to the insolubility of the starch granules these materials are fairly easily removed by various wet-processing operations and the starch granulesuspension may be readily ,dewatered to form a cake in a filter and thenwashed to a highdegree of purity and dried without significant losses or changes in physical state. Due to its comparative ease of separation and purification in granular form, starch is a relatively low cost material, and is consequently utilized in large quantities in numerous industrial applications.

Since naturally occurring starch does not have the required physical characteristics necessary for utilization in many industrial applications various chemical treatlow or moderate temperatures or at high temperatures in the presence of a limited proportion of water which is insufficient to swell the starch. The chemical reactions which can be conducted on unswollen granule starch in low temperature suspensions are particularly convenient andeconomical since the starch may be treated at some stage during its wet-processing, then dewatered, washed, and dried in the same manner as untreated starch. The large scale economical production of such modified starches is possible because of the insolubility of the starch granules at low or moderate temperatures and the relative ease with which they may be dewatered and dried. If starch granules once become swollen or gelatinized it is impossible to reverse the action and obtain the Original cold-water insoluble granule state. It is very difficult and costly to purify and dry starch which is in the swollen or gelatinized state. Such starch binds water too tenaciously to allow dewatering in commercial filters. While a relatively small amount of starch is commercially processed by gelatinizing or heated rolls and grinding the dried film to.a powder, the product does not have These granules are "2,773,057 Patented Dec. 4, 1956 the original, cold-water insoluble, granule form, but rehydrates immediately when wet to form a paste which contains swollen aggregates of starch which result in a coarseness or rough texture and low adhesive power. Such products, when cooked with heat, do not attain the smoothness, homogeneity and adhesive power that is obtained when pastes are made by gelatinizing starch in its native gr-anule form. Such pre-cooked or pre-gelatinized starches require special processing equipment for their manufacture and have limited usage.

It has been known for many years that etherifying agents can be made to react monofunctionally with gelatinized starch to produce starch-ether derivatives having varying degrees of substitution of alkyl groups for the hydroxyl hydrogens of the starch. Practically all of these reactions are accomplished by the action of aqueous alkali such as sodiumor potassium hydroxide solutions. Since starch granules are readily swollen and gelatinized by relatively low concentrations of strong alkali in cold water and since the monofunctional substitution of ether groups in starch usually greatly increases the susceptibility of the starch to swelling by the action of heat or alkali, it has generally been considered impossible to obtain such ether derivatives in the unswollen, granule state when such reactions are conducted in water, except in the case of certain highly reactive, etherifying agents which require only very low concentrations of alkali to produce etherification, as indicated below. Therefore, due to the difliculty and high' cost of purifying and drying gelatinized starch, such swollen, etherified derivatives, though extensively described in patents and other scientific and technical literature, have not been produced and marketed to any great extent.

The present state of the art of producing monofunctionally substituted ether derivatives of unswollen, granule starch-is illustrated by U. S. Patent No. 2,516,633, in which the highly reactive alkylene oxides and halohydrins are reacted in water suspensions under conditions of temperature and alkalinity sufficiently low to preventswelling of the etherified product. The temperature and alkalinity recommended in the process disclosed in this patent ranges from 130 F. and .008 to .02 mole of NaOHper CsHmOs mole of starch, when such reactions are conducted in high solids water suspensions of starch. While such alkylene oxides or halohydrins will combine with unswollen, granule starch under these conditions, all attempts to secure useful starch ether derivativesby reacting monochlorine substituted hydrocarbons or monochlorine substituted fatty acid salts with starch under these Though it has been known for bine with gelatinized starch under conditions of high alkalinity to yield products with desirable paste characteristics, such gelatinized starch alkyl ether derivatives have not been produced commercially to any significant 1 extent because of the difiiculty and cost of purification and drying and because gelatinized, dried starch products do not have the commercial utility possessed by starch in its original granule form, as explained above. .There has therefore been a definite need for a method of securing alkyl ether derivatives of unswollen granule through etherification with the diflicultly hydrolyzable alkyl chlorides, since many of these compounds are relatively low in cost and abundant. To our knowledge no process for securing these results has heretofore been disclosed.

The object of this invention is the production of mono- I functionally substituted partial alkyl ethers of unswollen,

granule starch by reaction of monochlorine substituted I organic compounds reacting monofunctionally with starch in which the chlorine is attached to a single bonded carbon atom'in an aliphatic chain.

Another object of this invention is to prepare water suspensions of unswollen, granule starch containing sufficient dissolved alkali metal hydroxides to cause monochlorine substituted organic compounds, in which the chlorine is attached to a single bonded carbon atom, to combine with the starch to yield partial ether derivatives inthe unswollen, granule form.

A further object of this invention is to prepare monofunetionally substituted partial alkyl ethers of unswollen, granule-starch which are characterized by lowered swelling temperatures, increased rate of granule dispersion of cooking, increased paste translucency and cohesiveness, decreased tendency of their c ooked pastes to retrograde and form gels on cooling and ageing, and increased clarity and smoothness of films formed from their cooked pastes.

Further-objects and advantages will appear as the specification proceeds. V The invention is based on the discovery that certain monochlorine substituted organic compounds, for example methylchloride, ethyl chloride, benz yl chloride, allyl chloride, and sodium monochloracet ate 'will combine efficientlyand-at a relatively high rate with highly alkaline, unswollen granule starch when it is suspended in'water in high solids-concentrations at elevated temperatures. In addition, it has been discovered that very small proportions oflsuchetherifying agents effect considerable changes in'the paste and film properties of the starches so treated. Forexample, by themonofunctional etherification of unswollen, granule corn starch with front-.01

to, .06 mole of alkyl'ether groups per Cal-11005 mole of starch a product is obtained which gelatinizes at lower temperatures than regular corn starch and rapidly disintegrates, toward true. colloidal state when cooked. The cookedpastes of this product are characterized'by a high degree of translucency and cohesiveness as compared with the cloudy,,relatively. short or non-cohesive state of regular corn starch pastes. On cooling and ageing the cooked pastes of this product are relatively free from retrogradation tendencies and retain their translucent andcohesive state, while regular corn starch pastes rapidly become cloudy and then opaque and set to firm gels which resist, redispersion to their original fluid state. a

In order to accomplish a useful degree of etherificat-ion of starch by means of monochlorine substituted hydrocarbons and monochlorine substituted fatty acid salts we have found it necessary to conduct the reactions under conditions of temperature and alkalinity much higher than has heretofore been considered possible when treat in'g water, suspensions of unswollen, granule starch. s weliing or gelatinization of the etherified product is prevented by addition of suitable gelatinization inhibitors, preferably. sodium chloride, which is cheapand abundant and which is, inert to the action, of the reagents required in the process and which does, not produce undesirable thickening effects in high solids suspensions of unswollen, granule starch. Other gelatinization inhibitors, in general the salts of alkali metals (sodium, potassium, and lithium) v may be used, though care must be exercised infth'eir use in order to avoid; undersirable side reactions or thickening effects. For example, alkali metal; thiocyanathes, iodides, bromides, and salicylates will function as gelatinizatioh inhibitors when present in relatively low 1 7 concentrations but tend to gelatinize starch in high con centrations. Acid salts will function as gelatinization inhibitors but their use'is less desirable since alkali is consumed as the acidity of the salt is neutralized. Salts having other chemical properties such as oxidizing or reducing characteristics may be used though such chemical activity is not required in the present process Certain saltssuch as sodium tetraborate and sodium sulfate may be used, though their use is less desirable due to ckeni t j i l ds e ons of swollen r 4 granule starch. Salts which exhibit alkalinity when dissolved in water also function as'gelatinization inhibitors, though their effectiveness varies considerably.

More specifically, fairly satisfactory results can be obtained by employing sodium, potassium or lithium chlorides, carbonates, acetates, nitrates, or sulfates, but sodiurn chloride is by far the most desirable swelling in hibitor for the reasons given above.

While it has been previously known that sodium sul= fate, traces of which are sometimes present in oofnmer cial grades of starch, exhibits some tendency to inhibit swellingof starch, it has not been known that this property is common to alkali metal salts; or that by employing a suflicient amount of an alkali metal salt the swelling of starch can be inhibited to an extent great enough to permit unswollen, granule, starch to be etherified with a monochlorine substituted organic compound reacting mono-func i n y w th. the ta ch wi hou gelatinizing ar h- Sti les ha t b en su pectedthat inexpem sive sodium chloride is; the ideal salt for this purpose. As previouslyindicated rather stringent temperature and alkalinity conditions are required tohydrolyz e a chlorine ste attached to a single bondedcarbon atom in a mono chlorine substituted organic compound, and the starch must be .in an aqueous suspension for the etherification reaction to proceed at a satisfactory rate. Exposure of unswollen, granule starch to the combined action of high temperaturesand a highly alkaline aqueous medium, wherefthe temperature is high enough and the alkalinitystrorig enoughto promote the reactivity of the hydroxyl group of the starch molecules with mono-functionally reactingorganic monochlorides would have been expected to lead to the complete gelatinization of the starch long.

before the completion of the etherification reaction. In fact, this result was invariably obtained prior to the present invention. 7 'It is therefore surprising that the swelling and ultimate gelatinization of starch can be in-: hibited sufficiently by the use of an alkali metal salt to permit inexpensive reagents, such as methyl, ethyl, and allyl chlorides, to be reacted with unswollen, granule starch without gelatinizing the starch.

The eitherification of unswollen, granule starch is accomplished by the following general process: The. starch is suspended in water at a temperature below the normal'ge'latiniza'tion temperature range of the-starch. The gelatinization inhibitor may either be added to the water befor Or after the starch or it may be added simultaneously with thefalkali.v In' any case the inhibitor should be present as the alkali is added. The alkali is dis solved in water, cooled, and added 'with suflicient agitation of the starch suspension to insure rapid dispersion of the alkali. This is necessary in order to prevent localized extremely high concentrations of alkali which tend' t'o sweil afportio n of the starch before the alkaliis dispersed and uniformly distributed throughout the suspension, The suspension is. preferably prepared with a water-starch'ratio of 1,3 to 2.3 parts byweight of water to 1 part by weightof starch, The amount of alkali required in the'suspension will depend somewhat on the etherifyingagent to be used and the degree of 'substitution 'ofether gro-ups' which-is desired." The etherifying agent is then added-t0 the suspension and'the mixture agitatedat a' 'suitable temperature, preferably 40? to 65 C'.,' until the desired proportion-of etherifying agent'has reacted. When etherif-ying agents with low boiling points,such asltheflower allcyl chlorides, are used it' isnecessary to. conduct the reaction in closed, pressuretight; vessels or with-Jsuitable refluxing condensers. The course of thereaction may be determined by removing portions of the. suspensionat intervals and titrating with acid. to determine the amountof alkaliconsumedbyhy drolysis of. the chlorideradical of the etherifying 'agent.

When the desired proportion of etherifyin-g agent has reacted the,excess alkaliris; neutralized withacid'and' the th r fi d starch is. .dewatered either in. a simple gravity...

iv m amps? filtei? are yaciiiimfilten'purifiedby washingoutthej salt, and; dried. Theetherifiedstarchis ob ained inthe-original,;u nswollen, granule'form. t The etherifying agentswhich have been found to be reactiveto highly alkaline, unswollen.granule starch-and which produce starch ethers which are characterized by lowered swelling temperatures, increased rate of :gtanule dispersion on cooking, increased translucencyandmo: hesivenes of cooked pastes, decreasedretrogradation and gelling of. cooked pastes, and increasedfilm clarity an d smoothnessi are the monochlorine 1 substituted organic compounds reacting monofunctionally with starch and in which the chlorine is attached-to] a single-bonded carbon atom in an aliphatic chain. Single-bondedcarbon-atoms are defined ascarbon atoms to which four, atoms are attached by single bonds. For example, the carbon atoms in;rnethyl chloride iso-propyl chloride 31191 chloride to which the chlorine is attached are single-bonded carbon, atoms. These compounds will function in our processv and give the results described. On the other. hand, vinyl chloride 7 i i I 11- =o-01) chlorobenzene and acetyl chloride (H-(ii-O r H 7 01 will combine with alkaline, unswollen granule starch. by fsplittingoff the chloride radical and establishing a. adi etw ii ealph pna m 9i 39 ths if g agent and the starch rather than. reacting-through the sodium carboxy (-.CQONa) group. .Also,,a-ll yl chloride (C1--(|)O=CH) will, combine with alkaline, unswollen granule starch by splitting oif the chloride radical andestablishing a bond betwe'en'the. number 3 carbon atom of'the etherifying agent and the starch-rather than reactingflthrough: one of the double bo'ndcarbon atoms. Onthe'other hand; monohalogen substituted compounds .which contain .certain other reactive groups have been. found tov yield products with characteristics which areopposite to those obtained by etherification with monofunctionally reacting etherifying agents. For example, epich-lorohydr-in combines withalkaline, un'swollen granule starch to yield products which are characterized by greatly increased resistance to gelatinization by means of heat or alkali,an d greatly increased resistance to granule dispersion on cook ing at elevated temperatures. Many of the productsob tainedby etherifying starch with such reagents cannot be 'gelatinized by boiling water. In general, compounds which react 'rhonofun'ctionally with' alkaline, unswollen granule starch" by hydrolysis of a chloride radical are the required class of etherifying agents in the present process;

"One preferred class of ethe'rifying agents for use in the process of this invention can be: designated] as monoclrilorine-substit uted hydrocarbons containingjfrqm 1 to 10 carbon a'tor'nsand in-' whicli the chlorine atom-is at tached to a single bonded carbon atom in an open chain.

Included within this class are aromatic and alicyclichy-Z drocarbons having open side chains containing a chlorine atom, and open chan hydrocarbonsof both --the straght and'branched chaintypes. The open side'chainsof the aromatic and alicyclic hydrocarbons and the open chain hydrocarbons may be either" saturated or t lnsaturated pro-' vided the carbon atom to "whiclithe chlorine atom is 1 bonded is not bonded by an unsaturated linkage.

rated alkyl'monochlorides' containingffrom 1 m 5 car-- bon atoms and unsaturated alkyl monochlorides (contain ing from '3 to 5 carbon'atoms are especially desirable agents. Specific preferred agents are: methyl chloride," ethyl chloride, and allyl chloride. a

The present process aflfords 'ameans of introducing. various functional groups into starch. For example," sodium carboxy-methyl groups; may be introduced etherifying with sodium inonochlorar:etate. While sodium monochloracet-ate is preferred, other monochlorine; substituted saturated fatty acid salts can be employed.- Preferably, such etheri-fying iagents contain from 2 to '5' carbon atoms and are in the form of their alkali metal salts. By etherifying with allyl or methal-lyl chloride, groups containing double bonds may he introduced. Aromatic or cyclic groups may be introduced by etherify ing with aromatic or cyclic compounds containing a monochlorine" substituted aliphatic "side chain. "Un-r swollen granule starch containing small proportions of such groups attached through single ether linkages exhibit a wide variety of chemical and physical properties" and are useful in numerous industrial applications and;

as intermediates for conversion'to other unusual'and chloi'ine substituted 'etherifying agents in the aboveidescribed .process effects considerable change, in'the pastes;

of starches so treated. The use. ofan amount of etherii'ying agent of from .005 to .06 mole per CeHmQs mole of starch results in starches having improved properties. The use of lower alkyl monochlorides, such as saturated, qc l i c, subst u dm o s an unsa ra e mnnoch-lorgindsubstituted hydrocarbons containing upto '5 catbon atomsfi esultsin toweredgelatinization temperatures, increased paste cohesiveness and translucency, minimized retrograd ation andgelling tendencies, and increased clarity and smoothness'of dried films. In some cases high proportions are desirable though it is usually not. feasible to react "more. than .15 mole-of et'herifying agent per Cal-E1 95 mole lof'starch. I

Iheeainount of alkali required to cause the etherifying agentto combine :with starch 'varie's somewhat depending on the kind of ethenifyin-g agent which is used. Genenallygzrlkali inTexcessof-rhat. required to neutralize the acidityiof the chloride radical; as. it is removed during ctherification' is desirable for efficiently ethe'rifying sunswjollen, granule 'Ihe etheriiication of. alkaline, unswollen; granule ist-archwith methyl chloride is. accomplished with a lower proportion of alkali in excess of that required to neutralize the acidity of the chloride radical as it is removed than is required for etherification with homologs containing a greater number of carbon atoms. The messa e o va ious. functional roups i th ky ta a ect th ease with. which the. h ori rad c l may sc' plit o flby kal ne hydro ysis o ex mple, he c hs t cat o io alkaline, unswo n. g a e s arch with a l hlor d =(Cl 2Hz-CH;H2).- mcliched wit ra lowe prop rti n of lka i in ex es of that equir d toe tr ze h d y o he hlor e llad' fll nfi t s remo d: t a .is. oi ired o c ion u t rr nylsh o ide :.+CH2:O .3)- he rm,- tcrrcd amount f a ka i o be s r n o .1 o :8 mo cia ij met hy roxi e per 110. mole of starch T ll generally result in the prefenredexcess O ali o -9 per QsHro'Qs mole'of starch. Whilesuch high proport n s: ta a tend o g a in ze st r n h solid uspe sion; t e a ai n .oi' h a ch Q .v ethcrified pr is. prevented 'hytheaddition of'an-alkalimetal salt such,

as sodi m; h o au on mo a g-i c m. 1 to par y. we ht; o a t o 1 part y weight of i- Thejtjerrn falkali metal as used in this specification and claims is intended to cover. sodium, potassium, and it um, while e t rm .a m ta yd o i is nde ocov r; odium. po a s m, nd thium yd odi m and notas um yd o e P rr d- The-term starch asusedin this specification inclmies the ,Yanious varieties of starch and commonly manutactnredm difica ions th eo whic a e p od in v cold water insoluble, unswollen, granule form. The granule stru ture; of.-stah; p r sts. vmdu ins such modificati n:tr m ts; aq rwnye iqn fih ncili yr s. vie-sta h an hyps h orits oxida io a I e have ound hat. the; dif ere t, iet -0f rchand mod ficati ns. here wh h x st neccl h t r insolu le, n o le a u e orm. e pond.- t h p e nLr o css-vand: PQQQHCR e sult -o des ribe Asupireviously mentioned. the. ethe fica on. y. a ky halidcszof starch'which isswollen orn ore or less com: pletely. gelatinizedisoldimthe: art and such reactions couldcbe accomplishedby. using high proportions ofstrong alkali:orielevateduemperatures or bothsince filterability 60 ofzthe ethe'rified', starchaproductsis not required; In

the old.v process the preparation of .d ry, powdered forms ofstarch-etherderivatives usually required desolva'tion andzresultin'g. precipitation of the swollen or'ge'latiniz'edj productsfbyalcohols or. other. waterrniiscible liquids whichlh-ave no tendency to. swell; starch. The present process, however, affords a means of preparing alkyl? ether derivatives of-starch in the'unswollen, granule form which can 'be'- readily'purified washing on a filter and which ondry-ingare in a form similar to regular "commercial' starch is not requi red,- 'sinc e the product isnot solvate'dorv The temperature at which the etherifications-can be 1 5 mol of lk i me dr x de 'Desolvlat-ion'orprecipitation with alcohol swollen to the that woukl allow precipitation i c nducted -vary somewhat, depending-on the ease; of lhy short, non-cohesive character, which rapidly'ret-rograde and gel to semi-solids oncooling and aging. The tacky,

craneser the 'particii'lar ethefi g agent employed. In general, temperatures front 2 5 565? Qfaresuitable The inbnochlr ine substituted saturated aliphatic hydroeagrbonssuen {as the lower alkyl monoclilor-ides, and aromatic or alicyclic compounds containing a monochlorine substituted saturated aliphatic side chain are relatively 'difficul't "to hydrolyze. Therefore, when etheriryin 'aikatine; unswollen, granule starch with suchco'm poundsternperatures ranging from 40 to C. are preferable. More highly reactive monochlonides may be reacted at lower temperatures, such as 25 to 40 C., thoiigh hi-giher' terjnperatures are preferred because of the increased rate of react-ion. I The new'physical and chemical properties of certainu-nswollen, granule, etherderiva-tives of starch which can be prepared for the first time by the process" of this invention make them useful in numerous industrial applications. As previously described, we can for example, prepare partially etherified, unswollen granule starch in which the substituent groups bonded to the ether oxygen atoms are unsubstituted hydrocarbons, although previously no method was known for preparing such compounds. One type of new starch ether derivative having especially desirable properties are the partially etherified unswollen granule starches in which the substituent groups bonded to the ether oxygen atoms are hydrocarbon chains containing from 1 to 10 carbon atoms. Preferably, the substituent groups are open chain hydrocarbon groups, either saturated or unsaturated, containing from 1 to 5 carbon atoms. The lowered gelatinization temperatures, in: creased rate of dispersion toward true colloidal state during cooking, minimized gelling and retrograde Lion tendenoies, minimized hard size formation, and the increased film flexibility, smoothness, and ease. of desizing of the etherified granule starches containing short-chain alkyl groups make them especially well suited for use as textile warp sizes. The increased film clarity and smoothness of these.deniuatives make them useful for finishing textile fabricsi "The use of these derivatives in the sizing and coating of paper is advantageous because of their miniinize'd gelling and retrograding tendencies, clearer films, and greater receptivity of the sized paper to printing. The hydrocarbon chains can beintroduced into the starch molecule by etherification with, the corresponding monochlorinated hydrocarbon in the manner previouslydescribed in detail. i

Many of the granule starch saturated alkyl ether derivatives such as those in wh-ichthe alkyl substituents' contain from 1 to 5 carbon atoms, form-pastes when gelatin-ized which have an exceptionally high degree of cohesiveness of tack. This property isobtained in granule ethers of common cereal starches such as corn, wheat, or rice starch, which ordinarily gelatinize to form pastes of a cohesive nature of the gelatinized pastes of granule starch alkyl-ether derivatives together with their relative freedom from gelling and retrogradation tendencies make them-,very useful in, theforrnulation of adhesives. These derivatives arealso useful'as laundry starches because of theirease .of gelatinization, non-congealing paste characteristics, andtheir film smoothnessandflexibility, which result in less harsh finishes on fabrics and lessened ten eca a eta n in Etherification of granulestarch with unsaturated alkyl chlorides such as allyl or methallyl chloride results in derivatives which retain theunsaturated groups or double bonds between carbon atoms. These unsaturated groups are susceptible to various chemical actions such as oxidation, direct addition of halogens, etc. These derivatives are therefore useful as intermediates for the preparation of granule starches containing new and unusual combinations of functional groups The allyl and: methallyl ether.

derivatives of granule starch as prepared in the present 1 process also *gelatinizeatlower temperatures andform was:

cohesive, highly translucent pastes with minimized retro-. gradationand gellingcharac'teristics and their films .have' increased clarity, smoothness, and. ease of redissolvingg The unsaturated alkyl groups introduced into'the starch molecule preferably contain firom .3 to carbon atoms.

Granule starch ether derivatives prepared by etherifying by the present process with chlorine substituted fatty acid salts such as sodium monochloracetate or homologous compounds have the ability to become very highly hydrated when gelatinized and form pastes of very high viscosity. These derivatives are useful as thickenens in various industrial applications and as detergent adjuncts for preventing redeposition of soil. They are also useful as sizes and adhesives because of their cohesive, non-.

gelling paste characteristics. The chlorine substituted fatty acid subs-tituents introduced into the starch molecule preferably contain from 2 to 5 carbon atoms.

It will be understood that the etheri-fying agents falling within the scope of this invention as previously described may contain various functional groups. However, the

etherifying agents of this invention should not contain.

Example I To .a 43.5% dry substance water suspension of unmodified corn starch is added by weight of sodium chloride based on the water in the suspension. A cool, aqueous 17% solution of sodium hydroxide containingv 4% NaOH based on the starch solids in the suspension is added with suflicient agitation to insure rapid dispersion of the alkali throughout the suspension. The suspension is placedin gas tight vessel, the air above the suspension 2 '40 sure of 10-l5 lbs. per square inch above atmospheric. pressure is obtained at a temperature of 51 C. .The susevacuated to a 25" vacuum, and methyl chloride gas admitted to the vessel and temperature raised until a prespension is agitated at this temperature and methyl chloride admitted to maintain a pressureof 10-15 lbs. per square inch until .05 mole of methyl chloride per C6H1005 mole of dry starch has reacted within 8 'to 10 hours as determined by the amount of alkali consumed in the 'susf pension. The suspension is neutralized to a pH of, 5'. 0 with hydrochloric acid, dewatered to a solid cake ona suction filter, washed free of salt, and dried. The product is obtained in the original granule form. On'heating a neutral water suspension the methyl granule starch'starts to gelatinize at 62 C.-63 C. as compared with untreated, unmodifiedcorn starch, which starts to gelatinize at 65 C.-66 C. On continued heating, the methyl granule'starch derivative forms a cohesive, comparativelyj translucent paste, which on cooling has negligible retrogradation tendency and which remains fluid and translucent in concentrations at which a regular unmodified corn starch paste sets to a firm opaque gel.

\ Example 11 To a 41.8% dry substance suspension of unmodified corn starch is added"20% by weight of sodium chloride based on the water in the suspension. A cool aqueous 22% solution of sodium hydroxide containing 5% NaOH based on the starch solids in the suspension is added with suflicient agitation to insure rapid dispersion of the alkali throughout the suspension. The suspension is placed in a gas-tight vessel, the air above the suspensionevacuated to a 25" vacuum, and ethyl chloride gas admitted to the vessel and the temperature raised until a pressure of 1015 lbs. per square inch above atmospheric pressure is obtained at a temperature of 51 C. The suspension is i agitated at this temperature and ethyl chloride admitted to maintain a pressure of" 10-15 .lbs. per square inch for 10-15 hours until .05 mole of ethyl chloride per Cal-[1005' mole of starch has reacted, as determined by the amount of alkali consumed in the suspension. The suspension is neutralized to pH 5.0 with hydrochloric acid, dewatered to a solid cake on a vacuum filter, washed free of salt,

and dried to around 10% moisture. The product is obtained in the original granule form. On heating a neutral, water suspensionthe ethyl granule starch starts to gelatinize at a somewhat lower temperature than does regular unmodified corn starch, and on continued heating it forms a cohesive, comparatively translucent paste, which on cooling has considerably reduced retrogradation tendency and remains fluid and translucentin concentrations at which a regular, unmodified corn starch paste sets to a firm, opaque gel.

Example II I To a 43.5% dry substance suspension of unmodified corn starch in water is added 15% by weight of sodium;

chloride, based on the Water in the suspension. A cool, aqueous 20% solution of sodium hydroxide containing 5% byweight of NaOH based on starch solids in the suspension is added with suflicient agitation to insure rapid dispersion of the alkali throughout the suspension. Three percent by weight of normal propyl chloride based on starch solids is added to the suspension and the suspension is then agitated in 'a closed vessel at 51 C. for.

20-24 hours until, .04 mole of n-propyl chloride per C6H1005 mole of starch has reacted, as determined by 'the amount of alkali consumed. The suspension is then neutralized to pH 5.0 with HCl, dewatered to a solid cake on a vacuum filter, washed free of salt and dried to 10% moisture. The product is obtained in the original granule form. On heating a neutral water suspension of the n-propyl starch it forms a paste with greatly increased cohesiveness and translucency as compared with pastes of regular, unmodified corn starch, and which on cooling has greatly lowered retrogradation and gelling tendencies and remains fluid and translucent to concentrations at which a regular unmodified corn starch paste sets to a firm opaque gel.

' i Example IV The process described in Example III is conducted using 20% by weightof sodium chloride based on the water in the suspension,- a 30% sodium hydroxide solution containing 5% NaOH based on starch solids in the suspension, 4%by weight of n-amyl chloride based on starch solids, and a reaction temperature of 60 C. The

suspension is agitated at thistemperature for 20-30,

hours until .02 mole of n-amyl chloride per CeHroOs mole of starch has reacted, as measured by the alkali consumed. The suspension is then neutralized with HCl, de-

watered to a solid cake on a vacuum filter, washed free of salt, and dried. The product is obtained in the original granule form. On heating a neutral suspension of the product in water it gelatinizes to form a translucent, somewhat cohes'ive paste which on cooling remains in a smooth spreading condition. y

v Example V To 543.5% dry substance suspension of unmodified corn starch is added a mixture of 30% sodium hydroxide and 26%.sodium chloride containing 3% by weight of NaOH based on starch and 10% by weight of NaCl based on water in the suspension while agitating the suspension vigorously. Then 2.8% by weight of sodium mono chloracetate based on starch solids is added and the suspension agitated at 45 C. for 20-30 hours until .035 mole .of sodium chloracetateper C6H10O5 mole of starch has reacted, as measured by the amount of alkali consumed during the reaction. The suspension is neutralized to pH 5.0. with sulfuric acid, dewatered to a solid cake on a vacuum filter, washed free of salt and dried. The product isobtained in the original granule form. :On heating a '11 neutral suspension of 'the, product in water it starts to g elatinize'at 6 1"" C. to'62 C. and on'continued heating itforms an exceptionally translucent, 'cohesive'paste with exceptionally high viscosity which on cooling 'has negligi- .ble retrogradationtendencyandwhich remains fiuid'and To a 41.8%. dry substance suspension of unmodified corn starch is added 20% by weightof'sodium chloride based on the water in the suspension. A cool, aqueous 30% solution of sodium hydroxide containing 5% by weight-of NaOH based on the starch solids in the suspension isadded with suificientagitation to insure'rapid dispersion of the-alkali throughout the'suspension. Then 3.9% by weight ofbenzyl chloride based on starch solids isadded and the suspension agitated at-60 C. for 10-to 20 hours until sub'stantially all of the benzyl chloride :h'as reacted, as determined by the amount of alkali consumed during reaction. The suspension is neutralized with acid, dewatered-to a'solid cake on a'vacuum filter, washed free ofsalt,'and' dried. The product is obtained in the original granule form. :When this productis heated in a neutral suspension in water. it starts to gelatinize at-60-61 C. and'on continued heating forms a paste with greatly in creasedtranslucency and cohesiveness as compared with pastes ofregular unmodified starch and whichon cooling has considerably reduced gelling and retrogradation tendencies Example VII To a 38% solids water suspension of :high grade, high viscosity tapioca starch is added 5% by weight of sodium bromide based on the water. A cool, 26% 'KOH solution containing 3.5% by weight of alkali based on the starch is added slowly while agitating the suspension sufiiciently to prevent localized swelling of the starch by the alkali. Then 0.45% by weight of potassium monochloracetate is added, and the suspension agitated at '51" C. for l20 hours until .005 mole of potassium monochloracetate perCsHroOs mole of starch has reacted, as determined by the amount of alkali consumed during the reaction. The suspension is then neutralized to pH'-6;0 with hydrochloric acid, dewatered in a vacuum filter, washed free of salt, and'dried. The product isobtained in the original granule form. On heating a neutral water suspension'the-product'forms a paste with higher hot'and cold paste viscosity than does the original," untreated tapioca starch.

Example VIII .washed thoroughly with water and dried. The product isfobtained in the'original granule forrn; On heating a neutral Water suspension thisproduct starts to gelatinize at a temperature several degrees lower than does untreated corn starch and on continued heatingforrns a cohesive, translucent paste, which on cooling. retains .its cohesiveness and has negligible tendency to set to a 12 s'en' i=. solid. on aging. The ungelatinized granules of 'the product combinewith bromine by 'direct addition and rapidly 'de'colorize potassium permanganate solution at.

Example IX To a 42.6% starch solids suspension of an acid-modified, .m'edium-fluidity corn. starch taken from thin-boil conversion tanks just prior to filtering and drying is .032 mole of sodium monochloracetate per CsH oOs mole of starch has reacted, .as determined by the amount of alkali consumed during the reaction. The suspension is then neutralized with acid, dewatered in asuction filter, washed free of salt, and dried. The product is obtained in the original granule form. On heating a neutral water suspension this product gelatinizes at a temperatureseveraldegrees lower than normal gelatinization temperature of the original untreated starch. On continued heating it 'forms'a cohesive, translucent pastehaving considerably higher viscosity than pastes .of the original untreated starch in the same concentration. paste of this product flows when'cooled to 27 C., while .a 10% cooked paste of the original untreated starch sets to a rigid gel when cooled.

While in the foregoing specification specific embodiments of the process of this invention have been discussed in detail, it will be, apparent to those skilled in .the jartfthat many, of'the'details set forth canjbe varied widelywithoutdeparting from'the spirit of the invention.

We claim:

1. In amethod of producing partially etherified, filterable, granule starch, the step of reacting unswollen, granule-starch with a monochlorine substituted organic etherifying agent reacting monofunctionally with .starch and in which thejchl'orineatom isattached to a singlebonded carbon atom in analiphatic chain, said etherifying agentb'eing free 'of hydroxyl and'epoxy groups, said reactionb'eing :carried out in an alkaline aqueous reaction medium in the presence of a suflicient amount of an alkali metal salt capable of inhibiting ,gelatinization of starch so that said starch remains filterable during the course of said reaction, said alkali metal salt being selected from the group consisting of .sQdium, potas'sium, and-lithium, chlorides, carbonates, acetates, nitrates and sulfates.

'2. The step of claim 1 in which-saidetherifyingagent has -the characteristics designated in claim '1 and in addition. is -.selected from the group consisting of saturated alkyl chlorides containing from. '1 to 5 carbon atoms and unsaturated alkyl chlorides containing from 3 to.5 carbon tom .3.- The stepof claim 1 in whichsaidetherifying agent is further characterized. as a .monochlorine. substituted saturated fatty acid salt reacting monofunctionally with starch and in which the chlorine atom is attached to a single-bonded carbon atom.

4;" In a method "o'fproducing partially etherified, filterable granule starch, the steps 'of reacting unswollen, granule starch with a 'monochlorine substituted organic etherifying agent reacting monofunctionally with starch and in 'which the chlorine-atom is attached" to a singlebonded carbon'atom in an aliphatic chain, said etherifying agent beingfree of hydroxyl and epoxy groups; said 'reaction being carried out, by mixing said etherifying agent with an aqueous suspension of said starch while maintaining said. aqueous suspension at a ternperature ranging'from 25to C., said'starch suspension containing 'an alkali;metal'hydroxide and an 'alkalirnetal salt selected from "the group consisting 'of' sodium, potassium A 10% solids cookedand lithium hydroxides and salts, and regulating the concentrations of said alkali metal hydroxide and said alkali metal salt to promote said reaction while substantially preventing the swelling of said starch during the course of said reaction so that said starch remains filterable as it is etherified, said alkali metal salt being selected from the group consisting of chloride, carbonate, acetate, nitrate and sulfate salts of said alkali metals.

5. The method steps of claim 4 in which said alkali metal salt is a chloride.

6. The method steps of claim 4 in which said alkali metal salt is a carbonate.

7. The method steps of claim 4 in which said alkali metal salt is an acetate.

8. The method steps of claim 4 in which said alkali metal salt is a nitrate.

9. The method steps of claim 4 in which said alkali metal salt is a sulfate.

10. In a method of producing partially etherified, filterable granule starch, the steps of preparing an aqueous suspension of unswollen, granule starch containing from 1.3 to 2.3 parts by weight of water to each part by weight of starch, said aqueous suspension having dissolved therein an alkali metal hydroxide capable of promoting an etherification reaction and an alkali metal salt capable of inhibiting gelatinization of starch during the course of such a reaction, said alkali metal hydroxide and said alkali metal salt being selected from the group consisting of sodium, potassium and lithium hydroxides and salts, said alkali metal hydroxide being present in the range from about 0.1 to about 0.28 mole of hydroxide per C6H1005 mole of starch, said alkali metal salt being further selected from the group consisting of chloride, carbonate, acetate, nitrate, and sulfate salts of said alkali metals, said alkali metal salt being present in the range from about 1 to 6 parts by weight of said salt per part of alkali metal hydroxide, and reacting said unswollen, granule starch with a monochloriue substituted organic etherifying agent reacting monofunctionally withstarch and in which the chlorine atom is attached to a single-bonded carbon atom in an aliphatic chain, said etherifying agent being further characterized as being a compound selected from the group consisting of saturated alkyl chlorides containing from 1 to 5 carbon atoms and unsaturated alkyl chlorides containing from 3 to 5 carbon atoms, said reaction being carried out by mixing said etherifying agent with said starch suspension and heating said suspension to a temperature between about 25 to C. to partially etherify said unswollen granule starch without swelling starch to an unfilterable condition, said etherifying agent being reacted with said starch in an amount between about 0.005 to 0.15 mole of etherifying agent per CeHwOs mole of starch.

References Cited in the file of this patent Kerr et al. Jan. 31, 

1. IN A METHOD OF PRODUCING PARTIALLY ETHERIFIELD, FILTERABLE, GRANULE STARCH, THE STEP OF REACTING UNSWOLLEN, GRANULE STARCH WITH A MONOCHLORINE SUBSTITUTED ORGANIC ETHERIFYING AGENT REACTING MONOFUNCTIONALLY WITH STARCH AND IN WHICH THE CHLORINE ATOM IS ATTACHED TO A SINGLEBONDED CARBON ATOM IN AN ALIPHATIC CHAIN, SAID ETHERIFYING AGENT BEING FREE OF HYDROXYL AND EPOXY GROUPS, SAID REACTION BEING CARRIED OUT IN AN ALKALINE AQUEOUS REACTION MEDIUM IN THE PRESENCE OF A SUFFICIENT AMOUNT OF AN ALKALI METAL SALT CAPABLE OF INHIBITING GELATINIZATION OF STARCH SO THAT SAID STARCH REMAINS FILTERABLE DURING THE COURSE OF SAID REACTION, SAID ALKALI METAL SALT BEING SELECTED FROM THE GROUP CONSISTING OF SODIUM, POTASSIUM, AND LITHIUM, CHLORIDES, CARBONATES, ACETATES, NITRATES AND SULFATES. 